WO2016143864A1 - Article en verre - Google Patents

Article en verre Download PDF

Info

Publication number
WO2016143864A1
WO2016143864A1 PCT/JP2016/057613 JP2016057613W WO2016143864A1 WO 2016143864 A1 WO2016143864 A1 WO 2016143864A1 JP 2016057613 W JP2016057613 W JP 2016057613W WO 2016143864 A1 WO2016143864 A1 WO 2016143864A1
Authority
WO
WIPO (PCT)
Prior art keywords
tin oxide
oxide film
film
glass
glass article
Prior art date
Application number
PCT/JP2016/057613
Other languages
English (en)
Japanese (ja)
Inventor
啓明 岩岡
淳志 関
阿部　啓介
雄一 ▲桑▼原
Original Assignee
旭硝子株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Publication of WO2016143864A1 publication Critical patent/WO2016143864A1/fr

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/22—Surface treatment of glass, not in the form of fibres or filaments, by coating with other inorganic material
    • C03C17/23—Oxides
    • C03C17/245—Oxides by deposition from the vapour phase
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/30—Deposition of compounds, mixtures or solid solutions, e.g. borides, carbides, nitrides
    • C23C16/40—Oxides

Definitions

  • the present invention relates to glass articles.
  • a tin oxide film having a predetermined thickness and a predetermined surface property is provided on one main surface of a plate glass.
  • the glass article of the present invention has a main surface on the side provided with a tin oxide film having excellent antifouling properties, so that the window glass for houses used in harsh environments, roofs of public facilities and the like imparted with translucency It is suitable for building antifouling glass used for highway sound insulation walls.
  • Patent Document 1 An antifouling glass article in which water repellency and oil repellency are imparted to the surface of a glass substrate such as plate glass is known (see Patent Document 1).
  • a transparent conductive film having an electric resistance of 2 M ⁇ / ⁇ or less is formed on the surface of a glass substrate, and an organosilane and / or organosiloxane layer is formed on the transparent conductive film. Is formed.
  • the transparent conductive film having an electric resistance of 2 M ⁇ / ⁇ or less include a tin oxide film.
  • the organosilane and / or organosiloxane layer exhibits water and oil repellency.
  • a transparent conductive film having an electric resistance of 2 M ⁇ / ⁇ or less prevents the generation of static electricity that causes dust adhesion.
  • the antifouling glass article described in Patent Document 1 includes a step of forming a transparent conductive film having an electric resistance of 2 M ⁇ / ⁇ or less on the surface of a glass substrate, and an organosilane and / or an organosilane on the transparent conductive film. Since a process for forming a siloxane layer is required, cost reduction is difficult.
  • the antifouling glass article described in Patent Document 1 is a water repellent composed of organosilane and / or organosiloxane, and has a glass substrate surface on which a transparent conductive film having an electric resistance of 2 M ⁇ / ⁇ or less is formed. Since the antifouling layer is formed by the treatment, the durability and weather resistance are not sufficient, and the antifouling layer peels off over time, and the antifouling property cannot be exhibited over a long period of time.
  • a superhydrophilic film on the surface of a plate-like substrate such as plate glass for the purpose of imparting antifouling properties.
  • a titanium oxide film having a catalytic function is widely known.
  • the titanium oxide-based superhydrophilic film has a disadvantage in that it cannot exhibit antifouling properties in places where it is not exposed to sunlight or at night because it uses the photocatalytic action of titanium oxide.
  • the antifouling properties are impaired due to a decrease in the catalytic function of titanium oxide.
  • Patent Document 2 As another attempt to form a superhydrophilic film for the purpose of imparting antifouling properties, there is an attempt to coat the surface of a plate-like substrate such as plate glass using a coating solution containing silica fine particles (Patent Document 2). To 4). However, these coatings were not sufficiently antifouling.
  • the present invention aims to provide a glass article capable of imparting excellent antifouling properties at low cost in order to solve the above-mentioned problems in the prior art.
  • the present invention is a glass article in which a tin oxide film is formed on at least one main surface of a plate glass, and the tin oxide film is The film thickness is 10 nm or more and 150 nm or less, The arithmetic average roughness Ra of the film surface is 1 nm or more and 13 nm or less, There is provided a glass article characterized in that a ratio (PV / Ra) between a peak-valley value (PV value) on the film surface and the Ra is 15 or less.
  • the arithmetic average roughness Ra and Peak-valley value (PV value) of the film surface are based on the definitions defined in JIS B0601: 2001. Further, the maximum height roughness Rz described later is also based on the definition of the same standard.
  • an alkali barrier layer is preferably formed between the plate glass and the tin oxide film.
  • the glass article of the present invention preferably has a haze value change ( ⁇ Hz) of 3% or less before and after the soil adhesion test using JIS test powder (2 types) (JIS Z8901).
  • the glass article of the present invention preferably has a haze value (Hz) of 5% or less after the dirt adhesion test using a pollutant suspended water (JSTM J7602: 2003).
  • the glass article of the present invention preferably has a shielding coefficient (SC value) (ISO 9050) of 0.6 to 0.95 when the surface on which the tin oxide film is formed is the light incident side.
  • SC value shielding coefficient
  • the glass article of the present invention preferably has a visible light transmittance (ISO 9050) of 40 to 80% when the surface on which the tin oxide film is formed is the light incident side.
  • ISO 9050 visible light transmittance
  • the alkali barrier layer is preferably composed of SiO 2 and the thickness of the alkali barrier layer is preferably 20 to 50 nm.
  • the glass article of the present invention preferably has a haze value change ( ⁇ Hz) of 1% or less before and after the soil adhesion test using JIS test powder (2 types) (JIS Z8901).
  • the glass article of the present invention preferably has a haze value (Hz) of 5% or less after a dirt adhesion test using a pollutant suspended water (JSTM J7602: 2003).
  • the tin oxide film preferably has a thickness of 100 nm or less.
  • excellent antifouling properties can be imparted at low cost.
  • the glass article of the present invention on one main surface of the plate glass (specifically, on the outermost surface on the main surface, for example, the main surface of the plate glass on the outdoor side of various buildings and structures), the conditions described later A tin oxide film satisfying the above condition is formed.
  • the glass article of the present invention has a main surface on the side provided with a tin oxide film having excellent antifouling properties, so that the window glass for houses used in harsh environments, roofs of public facilities and the like imparted with translucency It is suitable for building antifouling glass used for highway sound insulation walls.
  • the tin oxide film formed on one main surface of the plate glass has a film thickness of 10 nm or more and 150 nm or less.
  • the film thickness of the tin oxide film is less than 10 nm, the arithmetic average roughness Ra of the film surface and the ratio of the peak-valley value (PV value) of the film surface to the Ra (PV / Ra) are described below. Therefore, the antifouling property due to the formation of the tin oxide film becomes insufficient.
  • Low-E (low-emission) glass used as residential window glass reduces the emissivity and reduces the amount of heat transfer due to radiant heat transfer.
  • a metal oxide thin film having a small volume resistivity such as tin oxide is formed on the inner main surface.
  • the film thickness exceeds 150 nm in order to reduce the emissivity.
  • the main surface on the side on which the tin oxide film is formed is the outdoor side.
  • the emissivity of the tin oxide film becomes small. By reducing the amount of movement, the heat shielding property deteriorates, which is a problem.
  • the film thickness of the tin oxide film exceeds 150 nm, the haze value increases and the appearance deteriorates, which causes a problem.
  • monobutyl trichloride (MBTC) and other organic tin raw materials that are preferably used as a tin raw material are relatively expensive. If the film thickness exceeds 150 nm, an increase in cost due to an increase in the raw materials used when forming the tin oxide film becomes a problem.
  • the thickness of the tin oxide film formed on one main surface of the plate glass is preferably 20 nm or more and 150 nm or less, more preferably 30 nm or more and 100 nm or less, and 40 nm. As mentioned above, it is especially preferable that it is 95 nm or less.
  • the tin oxide film formed on one main surface of the plate glass has an arithmetic average roughness Ra of 1 nm or more and 13 nm or less on the film surface.
  • the arithmetic average roughness Ra of the film surface is in the above range, there are moderate irregularities on the film surface, so the main surface on the side where the tin oxide film is provided is excellent in antifouling properties.
  • the arithmetic average roughness Ra of the film surface is less than 1 nm, the film surface has almost no irregularities and is in a smooth state, so that the antifouling property becomes insufficient.
  • the tin oxide film formed on one main surface of the plate glass preferably has an arithmetic average roughness Ra of 1 nm or more and 12 nm or less, preferably 2 nm or more and 8 nm or less. It is more preferable.
  • the tin oxide film formed on one main surface of the plate glass has a ratio between the peak-valley value (PV value) of the film surface and the arithmetic average roughness Ra of the film surface (PV / Ra) is 15 or less.
  • the ratio between the PV value of the film surface and Ra (PV / Ra) is in the above range, the film surface has moderate irregularities, so the main surface on the side where the tin oxide film is provided is excellent in antifouling properties.
  • the ratio (PV / Ra) of the PV value of the film surface to Ra is more than 15, the film has pores, and the film surface other than the holes has almost no unevenness and is in a smooth state. It is considered to be.
  • the antifouling property becomes insufficient.
  • the main surface of the plate glass on which the tin oxide film is formed preferably has a maximum height roughness Rz of less than 70 nm from the viewpoint of dirt adhesion and dirt removal.
  • the film thickness, the arithmetic mean roughness Ra of the film surface, and the ratio of the PV value of the film surface to the Ra (PV / Ra) among the main surfaces of the plate glass satisfy the above-mentioned conditions.
  • the main surface on the side where the tin oxide film is formed has excellent antifouling properties. In the present specification, the antifouling property is evaluated by the change in haze value before and after the two types of dirt adhesion tests described in Examples described later.
  • the glass article of the present invention has a haze value change ( ⁇ Hz) of 3% or less before and after the soil adhesion test (1) using the JIS test powder (2 types) (JIS Z8901) on the tin oxide film side. Preferably, it is 2% or less, more preferably 1% or less.
  • the dirt adhesion test (1) is performed on the tin oxide film side of the glass article.
  • the glass article of the present invention has a haze value (Hz) of 5% or less after the soil adhesion test (2) using the pollutant suspended water (JSTM J7602: 2003) on the tin oxide film side. Preferably, it is 4% or less, more preferably 3% or less.
  • the dirt adhesion test (2) is performed on the tin oxide film side of the glass article.
  • the film thickness of the tin oxide film formed on one main surface of the plate glass is larger than the film thickness of the tin oxide film formed on the main surface of Low-E (low emission) glass. Therefore, even if the main surface on the side where the tin oxide film is formed is used as the outdoor side and used as a roof for residential windowpanes or public facilities, the emissivity of the tin oxide film does not decrease and By reducing the amount of heat transfer due to heat, the heat shielding property is not deteriorated.
  • the emissivity is preferably 0.75 or more, more preferably 0.8 or more, and further preferably 0.85 or more.
  • a shielding coefficient (SC value) calculated based on ISO9050 is used as an index of heat insulation.
  • SC value when it is described as an SC value, it indicates a shielding coefficient calculated based on ISO9050.
  • the glass article of the present invention preferably has an SC value of 0.6 to 0.95, preferably 0.6 to 0.8 when the surface on which the tin oxide film is formed is the light incident side.
  • antimony may be contained in the tin oxide film as a dopant for the purpose of adjusting the SC value in the above range when the surface on which the tin oxide film is formed is the light incident side.
  • antimony is contained in the tin oxide film as a dopant, 0.02 to 0.3 mol% of antimony is preferably contained with respect to 1 mol of tin oxide (SnO 2 ), and 0.05 to 0.2 mol% is contained. More preferably, it is more preferably 0.1 to 0.15 mol%.
  • the glass article of the present invention has sufficient visible light transparency to be used as a roof of a house window glass or a public facility.
  • the visible light transmittance calculated based on ISO 9050 is preferably 40 to 80%, and preferably 50 to 70%. More preferably, it is more preferably 60 to 70%.
  • the haze value is preferably low when the surface on which the tin oxide film is formed is the light incident side. Specifically, the haze value is preferably 1.0 or less, more preferably 0.6 or less, and even more preferably 0.4 or less.
  • the glass composition of the plate glass used for the glass article of the present invention is not particularly limited, and can be appropriately selected according to the application of the glass article.
  • the following glass compositions are exemplified when used as building antifouling glass used for housing window glass used in harsh environments, roofs of public facilities that have translucency, and highway sound insulation walls, etc. it can.
  • the plate glass having a glass mother composition may contain a component other than the above as a minor component. Specific examples of such a trace component include TiO 2 and CeO 2 . These trace components may be contained in an amount of 1% or less in terms of mass% based on the oxide.
  • an alkali barrier film is interposed between the plate glass and the tin oxide film in order to minimize the diffusion of the alkali component from the plate glass to the tin oxide film. It is preferable to form the film because the antifouling property is improved.
  • the alkali barrier film formed for the above purpose include a SiO 2 film and a SiOC film. Among these, a SiO 2 film is preferable because it has excellent alkali barrier properties.
  • the film thickness is preferably 10 to 100 nm, more preferably 20 to 50 nm, and still more preferably 20 to 40 nm.
  • the tin oxide film satisfying the above-described conditions of the film thickness, the arithmetic average roughness Ra of the film surface, and the ratio of the PV value of the film surface to the Ra (PV / Ra) is obtained by using an atmospheric pressure CVD apparatus. It can be formed on one main surface.
  • the atmospheric pressure CVD apparatus the use of a transfer type atmospheric pressure CVD apparatus is preferable because it is suitable for mass production of the glass article of the present invention.
  • the formation of the tin oxide film using the atmospheric pressure CVD apparatus may be performed as on-line CVD for forming the tin oxide film subsequent to the production of the plate glass, and the tin oxide film is performed in a separate process from the production of the plate glass. You may implement as an off-line CVD method which forms.
  • a raw material gas containing a tin raw material is sprayed onto one main surface of a plate glass heated to a high temperature (for example, 550 ° C.).
  • a tin raw material it is preferable to use monobutyltin trichloride (MBTC) because it is easily available and easy to handle.
  • MBTC monobutyltin trichloride
  • water (H 2 O) and oxygen (O 2 ) are simultaneously sprayed on one main surface of the plate glass as auxiliary materials.
  • hydrogen chloride (HCl) may be simultaneously sprayed as an auxiliary material.
  • MBTC monobutyltin trichloride
  • the MBTC content in the raw material gas is preferably 2 mol% or less.
  • H 2 O, O 2 , and HCl used as auxiliary materials the H 2 O content relative to MBTC in the raw material gas is preferably 20 mol% or less, and similarly, the O 2 content relative to MBTC in the raw material gas.
  • the HCl content relative to MBTC in the raw material gas is preferably 1.5 mol% or less.
  • the arithmetic average roughness Ra of the tin oxide film surface and the PV value of the film surface are adjusted by the molar ratio of HCl and MBTC in the raw material gas and the molar ratio of H 2 O and MBTC in the raw material gas. it can.
  • the molar ratio of HCl to MBTC (HCl / MBTC) in the raw material gas is preferably 0 to 4, more preferably 0.01 to 3, and further preferably 0.01 to 2. preferable.
  • the molar ratio (H 2 O / MBTC) between H 2 O and MBTC in the source gas is preferably 0.1 to 100, more preferably 1 to 70, and more preferably 10 to 60. Is more preferable. Further, the molar ratio (O 2 / MBTC) of O 2 and MBTC in the raw material gas is preferably 1 to 100, more preferably 5 to 70, and further preferably 10 to 50. preferable.
  • Examples 1 to 12 are examples, and examples 13 to 19 are comparative examples.
  • presence or absence of SnO 2 film, SnO 2 film having a thickness, Ra according surfaces, PV, PV / Ra, dirt adhesion test (1) results, dirt adhesion test (2) results, the measurement results of the emissivity are shown in Table 1.
  • the dirt adhesion test (2) is the test result for Examples 7 to 13 and 18. In Table 1, the results of the dirt adhesion test (1) are shown as changes before and after the test (1), and the results of the dirt adhesion test (2) are shown as values after the test (2).
  • Example 1 A tin oxide film was formed on one main surface of the plate glass by an off-line CVD method using a transfer type atmospheric pressure CVD apparatus (belt conveyor furnace). Specifically, it is as follows. The belt conveyor furnace is heated to 580 ° C., and a plate glass having a thickness of 2 mm (soda lime silicate glass plate, trade name AS, manufactured by Asahi Glass Co., Ltd.) is conveyed in a fixed direction. On one main surface of this plate glass, MBTC , H 2 O, and O 2 were simultaneously sprayed to form a tin oxide film of 93 nm.
  • a transfer type atmospheric pressure CVD apparatus belt conveyor furnace
  • the supply amount of MBTC is 0.23 mol%, and H 2 O and O 2 have a molar ratio to MBTC (H 2 O / MBTC, O 2 / MBTC) of 20.01, 17. 95.
  • the surface of the formed tin oxide film was measured using an atomic force microscope (AFM) SPI-3800N / SPA400 (manufactured by SII Nanotechnology Co., Ltd.) with an operation area of 2.0 ⁇ m and an excitation voltage of 0.5 V. The arithmetic average roughness Ra and PV value of the film surface were determined.
  • AFM atomic force microscope
  • the plate glass after the tin oxide film was formed was cut to 5 cm ⁇ 5 cm, and then the surface on which the tin oxide film was formed was used as the light incident side using a haze meter HZ-V3 (manufactured by Suga Test Instruments Co., Ltd.). After measuring the haze value), a soil adhesion test (1) was performed using this sample.
  • ⁇ Stain adhesion test (1) Two types of 0.5 g of JIS test powder 1 (JIS Z8901) were sprinkled evenly on the surface on which the tin oxide film was formed using a tea strainer. After standing for 10 seconds, the sample was tilted by 135 °, the end of the sample was brought into contact with the ground twice at a speed of 10 cm / second from a height of 3 cm, the powder was dropped, and the haze value was measured again. This was repeated 10 times, and the value obtained by subtracting the initial haze value from the average value of the 8th, 9th and 10th haze values was defined as the change in haze value ( ⁇ Hz) before and after the soil adhesion test (1).
  • JIS Z8901 JIS Z8901
  • the emissivity was calculated
  • the main surface on the side on which the tin oxide film is formed is on the outdoor side, so if the emissivity is small, the amount of heat transfer due to radiant heat transfer is reduced, so that the heat shielding property is rather reduced. Getting worse.
  • Example 2 Before forming the tin oxide film on one main surface of the plate glass, the same procedure as in Example 1 except that as the alkali barrier film, an SiO 2 film was formed as follows and a tin oxide film 90 nm was formed. Carried out. A belt conveyor furnace is heated to 580 ° C., and a plate glass (soda lime silicate glass plate, trade name AS, manufactured by Asahi Glass Co., Ltd.) is conveyed in a certain direction. One main surface of the plate glass is coated with silane (SiH 4 ), and, by blowing O 2 simultaneously, thereby forming a SiO 2 film 30 nm.
  • silane SiH 4
  • Example 3 In the formation of the tin oxide film, the same procedure as in Example 1 was performed, except that HCl was simultaneously sprayed in addition to MBTC, H 2 O, and O 2 to form a tin oxide film of 90 nm.
  • the supply amount of MBTC is 0.23 mol%, and H 2 O, HCl, and O 2 have a molar ratio to MBTC (H 2 O / MBTC, HCl / MBTC, O 2 / MBTC), respectively. 20.01, 0.93, and 17.95.
  • Example 4 Example 3 except that a SiO 2 film was formed as an alkali barrier film and a tin oxide film 88 nm was formed as an alkali barrier film before forming a tin oxide film on one main surface of a plate glass in the same procedure as in Example 2. The same procedure was performed.
  • Example 5 The same procedure as in Example 3 was performed except that the molar ratio of HCl to MBTC (HCl / MBTC) was changed to 3.03 to form a tin oxide film 73 nm.
  • Example 6 Example 5 except that a SiO 2 film was formed as an alkali barrier film and a tin oxide film 74 nm was formed before forming a tin oxide film on one main surface of a plate glass in the same procedure as in Example 2. The same procedure was performed.
  • Example 7 The supply amount of MBTC and 0.09 mol%, relative to MBTC, H 2 O, and the molar ratio of O 2 (H 2 O / MBTC , O 2 / MBTC) a, respectively, as 54.0,48.5 The same procedure as in Example 1 was performed except that the tin oxide film 41 nm was formed. Further, the soil adhesion test (2) was performed on Example 7 and Examples 8 to 13 and Example 18 described below.
  • Example 8 A procedure similar to that in Example 7 was performed except that a SiO 2 film was formed as an alkali barrier film before forming a tin oxide film on one main surface of the plate glass in the same procedure as in Example 2.
  • Example 9 The supply amount of MBTC was 0.09 mol%, and the molar ratios of H 2 O, HCl, and O 2 to MBTC (H 2 O / MBTC, HCl / MBTC, O 2 / MBTC) were 54.
  • the same procedure as in Example 3 was performed except that a tin oxide film of 40 nm was formed as 0, 1.3, and 48.5.
  • Example 10 The same procedure as in Example 9 was performed except that a SiO 2 film was formed as an alkali barrier film before forming a tin oxide film on one main surface of the plate glass in the same procedure as in Example 2.
  • Example 11 A procedure similar to that of Example 9 was performed, except that the molar ratio of HCl to MBTC (HCl / MBTC) was changed to 2.5.
  • Example 12 A procedure similar to that in Example 11 was carried out except that a SiO 2 film was formed as an alkali barrier film before forming a tin oxide film on one main surface of the plate glass in the same procedure as in Example 2.
  • Example 13 Without forming a tin oxide film on the surface of the plate glass, the surface of the plate glass was observed with an atomic force microscope (AFM), and the arithmetic average roughness Ra and PV value of the film surface were determined from the obtained micrograph. .
  • AFM atomic force microscope
  • Ra and PV value of the film surface were determined from the obtained micrograph.
  • two types of dirt adhesion tests were carried out using this sample in the same procedure as in Example 1. did.
  • Example 14 In the SiO 2 film forming the same procedure of Example 2, on one main surface of the glass sheet, as an alkali barrier film, after forming the SiO 2 film, the SiO 2 film was observed by an atomic force microscope (AFM) From the resulting micrograph, the arithmetic average roughness Ra and PV value of the film surface were determined. Moreover, after cutting the plate glass after forming the SiO 2 film into 5 cm ⁇ 5 cm, measuring the haze value (initial haze value) using a haze meter with the surface on which the SiO 2 film is formed as the light incident side, Two types of soil adhesion tests were carried out using the samples in the same procedure as in Example 7.
  • Example 15 The same procedure as in Example 3 was performed, except that the molar ratio of HCl to MBTC (HCl / MBTC) was changed to 6.99. A tin oxide film was hardly formed on one main surface of the plate glass.
  • Example 16 The same procedure as in Example 15 was performed except that a SiO 2 film was formed as an alkali barrier film before forming a tin oxide film on one main surface of the plate glass in the same procedure as in Example 2. A tin oxide film was hardly formed on one main surface of the plate glass.
  • Example 17 For a commercially available Low-E glass having a tin oxide film formed on one main surface of a plate glass, the arithmetic average roughness Ra and PV value of the tin oxide film surface were determined in the same manner as in Example 1.
  • an SiOC film is formed as an alkali barrier film between one main surface of the plate glass and the tin oxide film.
  • Example 18 when a tin oxide film is formed on one main surface of a plate glass, a raw material gas containing a tin raw material is sprayed on one main surface of the plate glass heated at a temperature higher by about 150 ° C. than the other examples. It is a thing.
  • Example 19 an SiO 2 film is formed as an alkali barrier film between one main surface of the plate glass and the tin oxide film. Further, in the same procedure as in Example 1, changes in haze value ( ⁇ Hz) and emissivity before and after the soil adhesion test (1) were performed were measured. For Example 18, the haze value change ( ⁇ Hz) before and after the soil adhesion test (2) was measured in the same procedure as in Example 7.
  • the film thickness of the tin oxide film is 10 nm or more and 150 nm or less, the film surface Ra is 1 nm or more and 13 nm or less, and the PV / Ra is 15 or less.
  • the haze value change ( ⁇ Hz) before and after the implementation was 3% or less, and the antifouling property was excellent.
  • Examples 2 , 6, 8, 10, and 12 in which the SiO 2 film was formed as an alkali barrier film between the plate glass and the tin oxide film were particularly excellent in antifouling property.
  • the haze value (Hz) after the dirt adhesion test (2) was 5% or less, and it was confirmed that the antifouling property was excellent.
  • the emissivity is high and is 0.75 or more, even when the main surface on the side where the tin oxide film is formed is used as the outdoor side, the heat shielding property is deteriorated. There is no.
  • Example 13 In which the tin oxide film was not formed on the surface of the plate glass and Example 14 in which only the SiO 2 film was formed as the alkali barrier film, the Ra on the film surface was less than 1 nm. The haze value change ( ⁇ Hz) was over 3%, and the antifouling property was poor. In Example 13, the haze value (Hz) after the soil adhesion test (2) was performed was over 5%, and it was confirmed that the soil resistance was poor. In Examples 15 and 16, in which the tin oxide film was hardly formed on the surface of the plate glass and Ra was less than 1 nm, the change in haze value ( ⁇ Hz) before and after the soil adhesion test (1) was more than 3%. Dirty.
  • Example 17 and 19 using a commercially available Low-E glass in which a tin oxide film is formed on one main surface of a plate glass the emissivity is small because the film thickness of the tin oxide film is more than 150 nm. Since it becomes less than 3, when the main surface on the side where the tin oxide film is formed is used as the outdoor side, the heat shielding property is deteriorated.
  • Example 18 using a commercially available Low-E glass in which a tin oxide film was formed on one main surface of a plate glass PV / Ra on the film surface exceeded 15; therefore, before and after the soil adhesion test (1) was performed. The haze value change ( ⁇ Hz) was over 3%, the haze value (Hz) after the soil adhesion test (2) was over 5%, and the antifouling property was poor.
  • excellent antifouling properties can be imparted at low cost.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Metallurgy (AREA)
  • Mechanical Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)
  • Chemical Vapour Deposition (AREA)

Abstract

L'invention concerne un article en verre qui permet d'appliquer d'excellentes propriétés antisalissure à faible coût. L'article en verre comprend un film d'oxyde d'étain formée sur l'une des surfaces principales d'une plaque de verre, et est caractérisé en ce que le film d'oxyde d'étain présente une épaisseur de 10 à 150 nm, une rugosité moyenne arithmétique Ra de la surface de film de 1 à 13 nm, et un rapport (PV/Ra) entre la valeur pic-vallée (valeur PV) et Ra de la surface du film de 15 ou moins.
PCT/JP2016/057613 2015-03-10 2016-03-10 Article en verre WO2016143864A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015046861A JP2018076187A (ja) 2015-03-10 2015-03-10 ガラス物品、および、その製造方法
JP2015-046861 2015-03-10

Publications (1)

Publication Number Publication Date
WO2016143864A1 true WO2016143864A1 (fr) 2016-09-15

Family

ID=56879511

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2016/057613 WO2016143864A1 (fr) 2015-03-10 2016-03-10 Article en verre

Country Status (3)

Country Link
JP (1) JP2018076187A (fr)
TW (1) TW201637858A (fr)
WO (1) WO2016143864A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2019036289A (ja) * 2018-04-11 2019-03-07 クックパッド株式会社 販売支援システム、管理装置、及び販売支援方法
JPWO2022114038A1 (fr) * 2020-11-27 2022-06-02

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005190700A (ja) * 2003-12-24 2005-07-14 Asahi Glass Co Ltd 透明導電膜付き基板とその製造方法
WO2005110599A1 (fr) * 2004-05-13 2005-11-24 Nippon Sheet Glass Co., Ltd. Film stratifie photocatalytique
JP2006312230A (ja) * 2005-04-08 2006-11-16 Ohara Inc 基板および基板の研磨方法
JP2009221095A (ja) * 2008-02-19 2009-10-01 Asahi Glass Co Ltd Ｅｕｖｌ用光学部材、およびその平滑化方法
WO2012144237A1 (fr) * 2011-04-21 2012-10-26 Hoya株式会社 Procédé pour fabriquer une ébauche de verre pour disque magnétique, procédé pour fabriquer un substrat en verre pour disque magnétique, ébauche de verre pour disque magnétique, substrat en verre pour disque magnétique et disque magnétique

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2005190700A (ja) * 2003-12-24 2005-07-14 Asahi Glass Co Ltd 透明導電膜付き基板とその製造方法
WO2005110599A1 (fr) * 2004-05-13 2005-11-24 Nippon Sheet Glass Co., Ltd. Film stratifie photocatalytique
JP2006312230A (ja) * 2005-04-08 2006-11-16 Ohara Inc 基板および基板の研磨方法
JP2009221095A (ja) * 2008-02-19 2009-10-01 Asahi Glass Co Ltd Ｅｕｖｌ用光学部材、およびその平滑化方法
WO2012144237A1 (fr) * 2011-04-21 2012-10-26 Hoya株式会社 Procédé pour fabriquer une ébauche de verre pour disque magnétique, procédé pour fabriquer un substrat en verre pour disque magnétique, ébauche de verre pour disque magnétique, substrat en verre pour disque magnétique et disque magnétique

Also Published As

Publication number Publication date
TW201637858A (zh) 2016-11-01
JP2018076187A (ja) 2018-05-17

Similar Documents

Publication Publication Date Title
JP4955563B2 (ja) バリヤー被覆をもつ物品及びそのような物品を製造する方法
KR100735763B1 (ko) 규소 유도체 층을 구비한 투명 기판과 상기 기판을 사용하는 방법
CA2626843C (fr) Materiau anti-salissures et son procede d'obtention
CA2755003C (fr) Revetement en film mince et son procede de fabrication
US20050221098A1 (en) Substrate with a self-cleaning coating
EP3203273B1 (fr) Plaque de verre avec revêtement à faible réflexion, substrat de verre, et dispositif de conversion photoélectrique
KR101774611B1 (ko) 개선된 기계적 강도를 갖는 층으로 코팅된 유리 기판
PT1497234E (pt) Substrato de revestimento auto-limpante
TWI600627B (zh) 具有低片電阻、平滑表面及／或低熱發射之經塗覆玻璃
WO2006019995A2 (fr) Revetements d'oxycarbure de silicium aux proprietes hydrophiles durables
CN101925551A (zh) 具有溶胶-凝胶层的基材和生产复合材料的方法
US20160122238A1 (en) Solar control glazing
US20130032202A1 (en) Photocatalytic material and glass sheet or photovoltaic cell including said material
WO2016143864A1 (fr) Article en verre
WO2017119279A1 (fr) Élément en verre
US20140338749A1 (en) Photocatalytic material and glazing or photovoltaic cell comprising said material
Carmona et al. Protective silica thin coatings for historical glasses
TW200811075A (en) Anti-dazzling glass and method for producing anti-dazzling glass
JP6468195B2 (ja) 薄膜形成方法およびコーティングガラス
JP2005330172A (ja) ガラス板およびその製造方法、低反射性透明ガラス板、低反射性透明導電基板およびその製造方法、ならびに、低反射性透明導電基板を用いた光電変換素子
WO2023136000A1 (fr) Article en verre avec revêtement facile à nettoyer
JP7283530B1 (ja) 積層膜付き基材
WO2022255201A1 (fr) Substrat avec film stratifié
JP5992993B2 (ja) 低い粗さの層を有するガラス基材
Hammer et al. Improvement of the chemical resistance of zirconium fluoride glasses coated with a Tiron® modified tin oxide layer prepared by the sol–gel process

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 16761830

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 16761830

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP